本研究的主要目的是以電化學沉積技術與自主裝單分子膜表面改質
技術來開發一簡單、低溫的製程以製備應用於染料敏化太陽能電池上之鉑
對電極，其中電化學沉積技術包含了無電電鍍與電鍍兩種方式。
在無電電鍍沉積的製程上， 吾人配合適當的表面改質技術
(3-(2-Aminoethylamino)propylmethyl-dimethoxysilane (Me-EDA-Si))成功開
發出一低溫濕式製程，可製備出具有高度選擇性的鉑對電極於透明導電玻
璃上。吾人透過螢光顯微鏡、接觸角測試與原子力顯微鏡分析，發現
Me-EDA-Si 可成功的改質於透明導電玻璃上，此外，本研究同時利用高解
析電子能譜儀來分析每一步驟的改質結果，證明鈀觸媒可成功的接於導電
玻璃上以催化無電鍍的進行，因而發現經無電電鍍沉積的薄膜呈現粗糙的
表面而提高了鉑觸媒表面催化反應的活化位置。因此利用無電電鍍所製備
出的鉑對電極所組裝而成的染料敏化太陽能電池具有較利用濺鍍法所製
備之鉑對電極所組成的電池有較高效率。
而在電鍍製程的開發上，吾人成功的利用直接電鍍法在含有添加劑
Me-EDA-Si 的電鍍液中於30 秒內製備出一同時具有低電子轉移阻抗、較
少的白金含量與高活性面積的鉑對電極。吾人也發現，利用Me-EDA-Si
作為電鍍添加劑時，可以提高電鍍的電流效率且可以抑制半圓形的白金晶
粒成長，因此可得到較高比表面積的鉑電極。此外，將此利用電鍍法所製
備之鉑對電極組裝成染料敏化太陽能電池，吾人發現在Me-EDA-Si 添加濃
度為0.01 vol%時，其效率可達7.39%遠高於利用濺鍍法所製備之鉑對電
極。
使用電鍍法製備白金對電極的過程中，我們發現添加劑具有加速電鍍
並抑制半圓形晶粒成長的效果，所以在最後一部分，我們利用電化學實驗
IV
來了解添加劑對白金在電鍍時成核與成長機制的變化。根據電流-時間的變
化曲線和成核、成長機制模擬的結果發現，在較高白金濃度的情況下，添
加少量的Me-EDA-Si 具有幫助瞬間(instantaneous)成核的效果。相反地，
過量的添加劑會使得成核機制朝向逐步(progressive)成長。

In this study, we aim to develop a simple, low temperature process to
fabricate the Pt counter electrodes for dye-sensitized solar cells (DSSCs) based
on electrochemical deposition techniques including electroless deposition
(ELD), electrodeposition (ECD) and surface modification of self-assembled
monolayers (SAMs).
By electroless deposition, a cost-effective and low- temperature wet
process to coat Pt on counter electrode has been developed with superior
coating selectivity by means of self-assembly monolayers modification and
electroless deposition techniques. Images of fluorescent test and atomic force
microscope measurements demonstrated that 3-(2-Aminoethylamino)
propylmethyl- dimethoxysilane (Me-EDA-Si) was homogeneously grafted on
FTO surface and XPS result proves that the palladium deposited on the FTO
surface initiates the electroless deposition. The Pt deposit so obtained exhibits
rough morphology and increased active sites. This method makes it easy to
deposit a Pt thin-film under ambient condition without the need for high
vacuum chamber. Moreover, the so-prepared DSSC exhibits improved
performance compared to the DSSC with a sputtered Pt counter electrode.
In the case of electrodeposition, Pt counter electrodes with low
charge-transfer resistance (Rct), low Pt loading and high active surface area can
be obtained within 30s by using the direct-current deposition in the presence of
3-(2-Aminoethylamino) propyl -methyldimethoxysilane (Me-EDA-Si) as an
II
additive. The addition of Me-EDA-Si can not only enhance the current
efficiency but also inhibit the growth of semicircle-like grains, thus resulting in
Pt electrode with high active surface area. Consequently, the dye-sensitized
solar cells (DSSCs) fabricated with so-prepared Pt electrodes exhibited cell
efficiency of 7.39% while 0.01 vol% Me-EDA-Si was added, which is much
superior to that with sputtered-Pt electrodes under the same assembly
conditions.
In the last part, we would like to know how additive affects the Pt
nucleation and growth mechanism on the FTO surface since the additive
seemingly acts as an accelerator during Pt electrodeposition by studying the
FESEM images of electrodeposited-Pt electrode fabricated from a plating bath
containing Me-EDA-Si. According to the current-time transients experiments
and S-H theory model simulation, we found that Me-EDA-Si functions as
accelerator to promote nucleation with low concentration of additive under
high precursor concentration. By contrast, excess additive tends to influence
the nucleation of Pt deposition towards to progressive mechanism.

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